Process of converting oils



A. M. McAFEE.

PROCESS OF CONVERTING OILS.

APPLICATION FILEDYSEPT. so. 1913.

1,424,574,, Patented Aug. 1, 1922.

awe/MM snares earner strains at. lidoAEEE, or Bayonne, new JERSEY, assrenon ro'ennr nnrrmite consent, or rrr'rsanaen, rnnnsrnvama, a o'oaroaarron or'rnxas.

success or Qonvnarrne onus.

assesses Patented Aug. 1, i922.

application filed september 80, 1913. Serial No. 792,615.

To all to lwm it may concern Be it known that. I, ALMER MCDUFFIE- MCAFEE, a citizen of the United States, ro siding at Bayonne,.in the county of Hudson and State of New Jersey, have invented certain new and useful Improvements in Procgasoline to the exclusion of other products and in general of cleanly and completely converting higher'boiling petroleum oils into lower boiling oils, wherein a liquid body of such a high boiling oil is subjected to a longcontinued heat at a temperature below cracking temperatures but sufiicient to cause boiling or ebullition in the presence of aluminum chlorid, the low boiling products formed being abstracted from said liquid body as fast as produced and proportionate quantities of fresh oil being advantageously added'tolsuch body to maintain its volume, (and thereby the concentration of the aluminum chlorid) constant; all as more fully hereinafter set forth and as claimed.

Crude petroleum' always contains high boiling and low boiling constituents in varying proportions. As these low boiling constituents are worth more than the high boiling constituents, the edort in any distillationis to increase the amount of low boiling oils yielded; to increase the amount of gasoline and burning oil. This is ordinar ly done by conducting some portion of the distilling operation in such a manner as to effect a destructive distillation or cracking of the high boiling oils. This yields more gasoline but of a lower grade. 'The naturally contained low boiling constituents of petroleum such as gasoline, are mostly saturated com'- pounds which need little treatment to render them of commercial grade while the low boiling products obtained by this cracking operation are unsaturated and oflow grade being foul smelling, tending to burn with production of smoke, soot, etc. The market value of low boiling oils however is now so high that cracking of the high boiling residual oil is pushedas far as possible, high heat and pressure belng resorted to for this purpose. At temperatures around 650 F and above, a considerable proportion of the oil, butnot all, can be cracked down to yield low boiling bodies without, such a far? economical and ready method of converting high boiling oils into low boiling products with a conversion which is, in contradistinction to the usual cracking methods, substantially complete, 80 to 85 per cent of my original oil reappearing in the form of a water white, sweet, low-boiling oil of substantially saturated character needing little or no refining with acid and being susceptible of direct marketing.

To this end I avail myself of aluminum chlorid as a catalytic agent for converting, or depolymerizing, the high boiling oils into low boiling products such as gasoline. As is well known, aluminum chlorid exerts vigorous actions upon many organic bodies; a fact which forms the basis of the ordinary F riedel & Crafts reaction, which is much used in laboratory practice, and particularly for synthesizing aromatic hydrocarbons of higher molecular weight from hydrocarbons of lower molecular weight with the aid of organic chlorids. Its use in the petroleum art has been attempted for various purposes but, owing to the lack of certain necessary conditions and precautions, without success. As stated, the action of aluminum chlorid on organic bodies is vigorous, and without a careful regulation of conditions, this action is apt to produce very irregular results. And the products which it makes in these actions it is very apt to destroy again, or convert into other bodies. The action is one tending to go-forward to an equilibrium or balance. Without careful control of conditions, aluminum chlorid has a marked tendency to produce resins and tar. For these reasons in these prior attempts in treating petroleum the result was that while some light oils were produced, there was a large production of gas and heavy oils; instead of the reaction going on solely to the production of light oils, as is desirable for the present purposes, 1

it gave large proportions of-undesirable byproducts.

' I have found that by suitable regulation of conditions and the observance of a number of v higher boiling oils into lower boiling oils with the production of substantially no tarrv or resinous bodies or byproducts of low commercial grade; and in particular that I can use it to produce a substantially complete conversion into gasoline of all higher boiling oils. The products are saturated compounds and have little or no power of absorbing iodin, a common test in this respect.

In this operation there should be maintained a substantially uniform concentration of the aluminum chlorid used in the body of oil undertreatment, while the low boiling roducts formed by its catalytic action must be removed from its sphere of influence as fast as formed to prevent retrogressive chan es. aluminum chlorid at a constant point the volume of oil under treatment should be replenished with new or fresh oil as fast as the low boiling materials formedare removed from it; the amount of addition corresponding to the volume of lowboiling products removed. Furthermore, the concentration of the aluminum chlorid must be substantially uniform and constant throu hout the whole body of oiland as ebullition and diffusion cannot berelied upon to pre serve this uniformity, and particularly. since aluminum chlorid tends to concentrate in or on insoluble coky bodies produced, the whole mass must be i kept in vigorous agitation throughout the process. With ordinary rotary stirrers a speed sufficient to keep the bottom of the apparatus clear of any sediment should be maintained. This agitation is a fundamental necessity for uniform results. Further, as aluminum chlorid is a rather Volatile body and begins to volatilize freely at temperatures above 365 F., the

temperature of the vapors at the point of exit from the system should not rise above 350 F. .With the vapor exit temperatures at'or below 350, the vapors of high boiling oil which tend to form, are condensed and returned and with them is returned any aluminum"- -chlorid which 'may vaporize. This is not only useful in maintaining the concentration of aluminum chlorid in the body of oil constant but has the further advantage that the condensing apparatus for the gasoline, etc. beyond the still is kept clear and. free and does not plug up. Aluminum chlorid tends to form compounds (hydrocarbon-addition products of aluminum chlorid or double compound of hydro carbon and aluminum chlorid) with the To maintain the concentration of hydrocarbons which, like aluminum chlorid itself, are volatile, and if these compounds of 500 F. in the body of oil is quite suitable for most high boiling oils. At 500 Fxgas oil,lubricating oil and most residual petroleum oils will in admixture with aluminum chlorid begin to boil vigorously in the present process. This boiling is incidental to the progress .of the reaction and is also useful in maintaining homogeneity of the body of oil and reagent. The lower the end boiling point of the higher boiling oil operated upon, the lower is the temperature necessary for conversion. The reaction takes placeat temperatures below the end boiling point of the higher boiling oil used. In general I find it best to operate between 500 and 600, oil temperatures, as

extremes. In the reaction of .aluminum chlorid with these high boiling residual oils anddistillates, in the production of gasoline, boiling and the formation of gasoline are vigorous between 500 F. and 600 F., a substantial amount of boiling, with the class of oils here contemplated, setting in above .470 F. At 500 F. with high boiling oils the gasoline forming reaction 1s not so fast as to be uncontrollable; it does not tendto become violent or to form undesirable byproducts; and' particularly where the low boiling bodies formed are removed from the sphere of reaction as fast as produced. This removal of the low boiling bodies from the influence of the aluminum chlorid substantially as fast as they are produced is advantageous. If allowed to remain in the presence of aluminum chlorid, the low boiling bodies may be resynthesized to high boiling bodies or they may be broken down into gas.

The oils and the apparatus used should be free of water or moisture and of air or dissolved oxygen. Both moisture and oxygen lead to the production of undesired side reactions, apart from the undesirable action of the moisture on the aluminum chlorid itself. For this reason, in treating crude petroleum it should be submitted to a period of preliminary distillation or heating, not onlyto get rid of the low boiling constituents naturally present but also to free the still and the oil of moisture. Where a high boiling residual oil is used, or a distillate, and it is transferred from another still teeters while hot, this preliminary heating or distillation is not necessarv; but if the high boiling oil used has been exposed to air or has been in storage, it is commonly better to heat it for some time prior to adding the aluminum chlorid. For the same reason the oil used in replenishing the body of oil under treatment is fed in hot or dry. A. test Under such circumstances, hydrochloric acid is only formed where, as is later described, a little chlorin is fed into the still during the operation. I

The present process may be used on any crude petroleum or on any high boiling residual oil, such as fuel oil, still bottoms, etc. High boiling distillates like gas oil and lubricating oil may be treated by the present process to make low boiling products.

The time of operation is a very important factor. If the heating be forced so as to give a rapid distillation, not only are highboiling bodies sent over with the low boiling, and aluminum chlorid or its compounds volatilized, but suflicient time is not given for the action of the-catalytic agent on the body of liquid oil under treatment.

The aluminum chlorid employed may be any commercial preparation but should be anhydrous. Any moisture present decreases the amount of eflective aluminum chlorid to that extent. The aluminum chlorid may be formed from hydrochloric acid or chlorin passed over metallic aluminum, or from chlorin passed over a mixture of alumina, such as bauxite, with carbon. The aluminum chlorid thus produced may be condensed and directly added to the still. Or the vapors of aluminum chlorid may be led directly into the still. The aluminum chlorid used may be mixed with or dissolved in the inflowing oil. At the end of the operation of converting the oil, as hereinafter described, the residual coke and aluminum chlorid form a black granular mass and this may be used as a source of aluminum chlorid for the reaction; the granular mass for this purpose being heated in any suitable vessel and a small amount of chlorin passed over it. In the presence of this gaseous chlorin, aluminum chlorid volatilizes. freely while in its absence it is hard to remove the aluminum chlorid from the granular coky mass. The aluminum chlorid may however be recovered in other ways. I

Some of the results of my inventlon may be obtained from the use of ferric chlorid and zinc chlorid; but they are not so active as the aluminum chlorid and are not as well adapted for the present purposes; the formation of low boiling oils from high boiling oils.

Any suitable type of apparatus may be employed for the present purposes. An ordinary cheese box type of still, provided with a vapor conduit having means for cooling by air or otherwise at one place and means for returning heavy oil vapors condensed therein to the body of oilin the still, may be used. The apparatus should be provided with an eficient stirrin mechanism and with means for adding Trash oil and datalyst from time to time or continuously.

In the accompanying illustration I have shown, mainly in vertical section and more or less diagrammatically, an apparatus of a t pe suitable for carrying out the descri ed process.

In this showing, element 1 designates as a whole a still which may be of iron or steel or other suitablematerial; Within this still is mounted a-stirring and agitating apparatus consisting of a revoluble shaft 2 carrying at its base a chain drag or other form of agitating device 3. It may be actuated by pinion a, driven from shaft 5. Near the base of the still is an outlet 6 which may be used for withdrawing fluid oil. The manhole 7 may be used for cleaning and withdrawing coky residues. The inlet 8 may be used for supplying oil. The manhole 9 may be used for supplying aluminum chlorid, etc. The furnace 10 may be used for supplying heat. Connected with the upper part of the still is conduit 11 leading to an air cooled condensing chamber or back trap 12 for the purpose of returning condensates of high boiling vapors. Beyond this condensing chamber the conduit 13 leads to another air cooled condensing chamber 14. At its base this chamber is provided with-an outlet 15 communicating with a reflux conduit 16. Above uncondensed vapors are led forward through 17 communicating with another air cooled condensing chamber 18. This air cooled condensing chamber 18 at its base has an outlet 19 leading back to the reflux device. Depression--20 in this line acts as an oil trap. Returning to the last named air cooled condensing chamber, vapors are led' from it through conduit 21 past thermometer 22. These vapors pass into and throughcooled condenser 23 cooled in any suitable way as immersion in water in tank 24.

The operation of this device is evident from the foregoing. The still 1 is charged with a suitable quantity of .oil and aluminum chlorid and distillation begun. High boiling oils and vapors are condensed and returned by the several air-cooled condensing means described. Distillation may be conducted at any rate desired and the temperature of the boiling mass of oil and aluminum chlorid will e that at which it will boil under atmosphericpressure, say, around 500 F. in the case of high boiling petroleum oils. The important point m conducting the operation is the temperature marked by thermometer 22. The temperature'as shown by the thermometer at this point should notrise above 350 F. If the thermometerremains at about 350 F., the vapors condensing in the condenser 23 will be gasoline and kerosene, which may be afterwards redistilled and separated. With a somewhat lower thermometer temperature at the point of exit of vapors from the distilling system, say, about 300 F., the distillate will all be good, clean commercial gasoline of a saturated character.

A suitable proportion of aluminum chlo-.

rid for the purposes of the present process is about 2 to 5 per cent of the body of oil under treatment. With large amounts of oil under treatment in a still, about 5 per cent is a good proportion. This proportion is relative to the amount of oil temporarily in the still and not to the whole amount of oil treated by a given amount of chlorid. Considering the amount of oil treated, in obtaining complete conversion with 5 per cent in the still, one part of aluminum chlorid will treat about 50 parts ofoil before losing high activity. With a less complete conversion it will of course treat much more.

Much depends on the character ofthe particular oil treated. I

By feeding a little chlorin into the still during the operation the period of activity of'the aluminum chlorid is considerably enhanced.

, In the treatment of oil by the described process, it is found that a single charge of aluminum chlorid may be used for two or three days continuously before losing its high activity. At about the end of the first day after the addition of a new charge of aluminum chlorid, the contents of the still exhibit a peculiar phenomenon. The vicosi ty of the charge in the still increases, comparatively suddenly, until the contents are so gummy and viscous that the rotation of the stirrer is attended with considerable difficulty. At this time more power should be applied and the stirrer forced to continue in rotation. In the course of an hour or so the high viscosity begins to disappear and the rotation of the stirrer once more becomes free. If the stirring is kept up con tinuously as described the activity of the aluminum chlorid continues substantially undisturbed throughout these changes. In about another day the aluminum chlorid begins to accumulate in coky granules which tend to settle out if the stirring is discontinned. The aluminum chlorid in these granules for a time preserves its activity but this gradually decreases. When these granules lose high activity, as evinced by an undue lessening of the flow of gasoline, etc, from the condensers, the granular residue should be removed and 'a fresh charge of aluminum chlorid placed inthe still. 01' the whole contents of the still may be dumped, the granules allowed to settle out and the oil replaced in the still. Or a fresh charge of aluminum chlorid may be added to. the mass in the still and the operation continued without removing the first or exhausted charge, and this may be continued until there is too much of an accumulation of coky material in the still. 4

The still may be provided with any suitable means for trapping and Withdrawing this granular residue and the granules removed continuously or from time to time, fresh aluminum chlorid being added to the contents of the still to correspond to the amount withdrawn with the granular material, the addition being in any-of the ways previously described.

The time factorin this reaction I regard as of high importance.- Any given petroleum oil or product is a complex of very many different hydrocarbons, many of which dilfer materially in their reaction with'aluminum chlorid and their speed of reaction therewith. In the described operation, any portionsof the oil which are slowly or diflicultly reactive with aluminum chloridare simply held in the still until the desired reaction takes place; when the products are at once removed. Those portions of the oil in the still, and of the oil fed to the still, which are quickly converted are of course as quickly removed from thesphere of reaction. Other portions more slowly reactive remain in the presence of the aluminum chlorid until the desired reaction takes place.

In operating upon the ordinary types of crude oils, residual oils, etc., I have found it a desirable speed of operation to distil in such a way that a distillate equivalent to about one-third of the volume in the still is formed every four hours; or, stated inan- 1 other way, so that the distillate per hour'- amounts to about 10 to 12 per cent of the volume maintained in the still. This volume should be so controlled as to spread the period of high activity of a charge of chlorid over at least 48 hours.

In the practicaloperation of the described process, I have obtained as high as 85 per cent conversion of a high boiling oil-\into. a I

low boiling oil. In normal operation perhaps 10 per cent of the oil is converted into gas and 5 per cent forms coke. The gas may be used in heating the still. There appears to be no formation of tar or resin and the residual granular coke containing the aluminum chlorid appears to be a clean product. 7

In operating in the manner described the distillate is free of chlorin and of aluminum chlorid. Where a current of chlorin is introduced, some hydrochloric acid is produced but this goes over with the vapors without uniting therewith and may be readily sep arated from the condensed oils. Unlike cracked gasoline and kerosene, the distillate is composed apparently Wholly of saturated compounds and suffers but little loss on refining or treatment with sulfuric acid. It gives little or no reaction with iodin. It is generally of such a character where the operation is conducted as described, as to require no refining and it may be sent directly into the. market without chemical treatment. If desired it may be given an alkali wash and particularly where free chlorin has been led into the still. The product coming from the still in the described operation, where'the vapor is led off at about 350 is what is known in petroleum refineries as naphtha and may be condensed as a whole or refractionated to give gasoline, solvents, (the grade of distillate marketed for use in varnish and the like as a substitute forturpentine and sometimes known as turpentine substitute) and kerosene. The kerosene and solvents fractions may then be again treated with aluminum chlorid to alford gasoline. Conversion of these fractions into gasoline is much quicker than that of the heavy oil originally treated. Or the gasoline, solvents and kerosene (illuminating oil) may be condensed separately in the usual manner from the vapors coming from the still. The kerosene fraction is good water-white oil, ascending the wick readily and burning with a clean flame. vKerosene and solvent fractions and the-like from ordinary distillation may be treated with the aluminum chlorid. The reaction occurs at lower temperatures when such distillates are treated than when higher boiling distillates, such as gas oilor the like, are treated.

By adjusting the temperatures at the exit from the still to the condenser at various degrees of course the main body of the distillate may be made of different character. By maintaining the temperature at the exit of the vapor at about 350, the main body of the distillate is gasoline. If the temperature of the vapors leaving the distilling system is lower, being at, say, about 300 F., the kerosene and solvents fractions are eliminated and the product of the vapors upon condensation is directly marketable as gasoline. By dropping the exit vapor temperatures the kerosene and solvents fraction reflux to the still and are again exposed to the action of the chlorid.

move some of these sulfur bearing compounds and thereby prolong the period of activity of aluminum chlorid. This acid treatment will also remove moisture.

The apparatus used maybe of iron, steel or "any other convenient material. Where the apparatus and materials are, as is desirable, drythere is no necessity of using clay, lead, copper, etc.

The operation may be conducted under vacuum, ordinary pressure, or pressure greater than atmosphere, but as a rule ordinary pressure is best. There is no necessity here, as in cracking, of raising the boiling point of the oil by pressure and high cracking temperatures are objectionable as unnecessary and as making the action of the aluminum chlorid too quick, violent and uncontrollable. A temperature of about 600 is about as high as is safe even with slow acting nearly exhausted aluminum chlorid. The oil temperature increases progressively as the chlorid loses activity; but generally with gas oil, lubricating oil, .still bottoms, etc., the temperature of ebullition will average around 500 F. i

The double chlorid aluminum and sodium may be employed. As stated, other chlorids, such as ferric chlorid and zinc chlorid may be employed, but their use is not as advantageousas that of aluminum chlorid. The same is true of a number of highly reactive chlorids, such as titanium chlorid, silicon chlorid, phosphorus chlorid, etc. Antimony pentachlorid acts as a chlorinating agent. The trichlorid is not very active. Aluminum chlorid is the best catalyzing agent for thedpurposes of this invention which I have use V In another and methodical operation, a battery of, say, 8 stills may be provided with connections between them for allowing fiow of oil through the series. In the first two stills, crude oil may be distilled, the water and the gasoline and the burning oil fractions naturally present in the crude oil being removed. The heavy oil coming from the second still in series may be led into a third still where it is treated with a small amount of aluminum chlorid, say 2 per cent. Here the easily convertible bodies are converted into gasoline, etc. and removed as vapor. Heavy oil from this No. 3 still may go into No. 4 where it is treated with a slightly larger charge of aluminum chlorid. Most of the aluminum chlorid in No. 3 will stay in the still and not flow forward with the oil. In No. 4 still a larger pro ortion of aluminum chlorid may be employe Heavy oil from this still goes into No. 5 and from No. 5 into Nos. 6,7 and 8 successively, there being a progressively increasing amount of aluminum chlorid in each successive still.

' Nos. 7 and 8 stills may for example be opcrating with as much as 5 per cent of alu-' minum chlorid, calculated on the amount of oil temporarily in the still. It will be obtreated with only a little aluminum chlorid,

comparatively] The aluminum chlorid for each still may be charged therein andthe exhausted chlorid removed therefrom in any of the ways previously stated. I

Some ofthe advantages of my invention may be attained by a simple distillation in the presence of aluminum chlorid. If, for example, a charge of crude oil be first distilled in the-ordinary way to freeit of mois ture and to regain'the gasoline and kerosene components naturally present, a suitable amount of aluminum chlorid, say 1 to 5 per cent of the. amount of oil in the still, may then be added and distillation resumed.

further quantity of gasoline and kerosene of excellent quality will be secured, the amount. depending on the activity and amount of the aluminum chlorid and the len th of heating. Conversion can be carrie as far, as may be'desired, even to distilling the charge to dryness. F or a partial conversion, aluminum chlorid may be used which has been elsewhere employed and has lost part of its activity, As before, the new gasoline and kerosene obtained are of saturated nature, giving little or no react-ion with sulfuric acid or iodin. Theresidual high-boiling material left in the still when such a proportion as may be desired has been converted and distilled, unlike resi- Y dues from oiLcracking operations, is also of excellent quality and may be used for the manufacture of lubricants, of paraffin, etc. It may be removed from the still, leaving a sludge of aluminum chlorid behind for treatment-of another portion of oil, and be treated with strong sulfuric acid. 'If removed from the still in the liquid condition it should not be allowed to become moist orbe contacted with aqueous solutions of chemicals prior to the sulfuric acid treatment. Instead of removing the residue from the still it maybe steam distilled therein;

chlorid to distillation temperature, separat-.

or the removed oil may be steam distilled in another still. Where steam distillation is used avoidance of moisture is not important. Steam distillation gives a good quality of oil which ma be worked up for lubricants, etc. If the 011 is removed and treated with sulfuric acid it may be afterwards washed,- neutralized with alkali and boneblacked or treated with fullersearth.

What I claim is r 1. In the treatment of petroleum oils the process 'which comprises establishing and maintaining abody ofsuch oil and anhydrous aluminum chlorid at a boiling temperature, removing from the vapors pro- :duced the vapors of oils of lower boiling point than that normal to, the oil of such body and condensing the removed vapors.

2. The process of converting'higherfboiling petroleum oils into lower boiling oils which comprises heating such a higher boiling oil togetherwith a catalytic chemical of the nature of aluminum chloridto boiling temperature, separating vapors of lower boiling oil formed from higher boiling oils, and condensing the vapors of the lower boiling oil.

' 3. The process of converting higher boil ing petroleum oils into lower boiling oil which comprises heating such a higher boiling o1l together with a catalytic metallic hallde to boiling temperature, separating vapors of lower boiling oil formed from lhlgher boiling oil, and condensing the vapors of the lower boiling oil.

4. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating such a'higher boilin ch orid" to boiling temperature, separating vapors of lower boiling oil formed from higher boiling oil, and condensing the vapors of the lower boiling oil.

5. The. process of converting higher boiling etroleum oils into lower boiling oil whic comprises heating such a higher boilin oil together with anhydrous aluminum ch orid to boiling temperature, separating",

vapors of lower boiling oil formed from higher boiling oil,'f and condensing the vapors of the lower boiling oil.

6. In the treatment of petroleum oils, the process which comprises catalyzing a body of high boiling oil by aluminum chlorid at a boiling temperature While removing vapors of lower boiling products as fast as produc'ed, the vapors prior to removal being cooled sufficient to condense and volatilized aluminum chlorid;

7. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating such a higher boiloil together with anhydrous aluminum ing vapors of lower boiling oil formed from oil together with a catalytic metallic return n the conversion of oils, the processwhich comprises heating a body of relatively high boiling petroleum' oil to about its boiling point in the presence of aluminum chlorid, vapors of low boiling oily bodies bein constantly removed and vapors of high boi ing bodies being constantly condensed and returned to said body.

9. In the treatment of petroleum oils, the process which comprises heating an oil for a time, adding anhydrous aluminum chlorid to the-hot oil and maintaining the mixture at the boiling point with constant removal of vapors of products of lower boiling point than said oil, such removal being at a temperature sufficiently low to ensure condensation of vapors of high boiling bodies.

10. In the treatment of petroleum oils, the process which comprises heating an oil for a time, adding anhydrous aluminum chlorid to the oil whlch has been heated and maintaining the mixture at the boiling point with constant removal of vapors of products of lower boiling point than said oil, such removal being at a temperature sufliciently low to insure condensation of aluminum chlorid vapors.

p 11. The process of making low boiling oils from high boiling petroleum oils which comprises heating a mixture of high boiling oil and aluminum chlorid to a temperature at which ebullition and a free development of vapors occur, removin the vapors and cooling the same to a point at which theyhave a temperature corresponding to the boiling point of the lower boiling oil desired, returning the condensate of higher boiling oils and any aluminum chlorid whichmay be present to the mixture and condensing the residual vapors of the low boiling oil desired.

12. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating such a higher boiling oil together with aluminum chlorid to distillation temperature, separating vapors of lower boiling oil formed from higher boiling oil, condensing vaporsof higher boiling oil formed together with aluminum chlorid, and returning the higher boiling oil and the aluminum chlorid to .the body of oil undergoing distillation.

13. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating such a higher boiling oil together with aluminum chlorid to a distillation temperature and under partial reflux.

14. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating a mixture of such her boiling oil and aluminum chlorid istillation temperature, allowing the products of the reaction to pass-to a condenser, maintaining the condenser at a temahi m..

perature not substantially' above 350 F.,

and passing vapors not condensed at this temperature from said condenser to a final condenser for condensation.

15. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating a mixture of such a higher boiling oil and aluminum chlorid to distillation temperature, allowing the products of the reaction to pass to a condenser, maintaining the condenser at a temperature not substantially above 350 F passing vapors not condensed at this tem-' perature from said condenser to a final condenser for condensation and separating and collecting the condensate from the condenser maintained at not substantially above 350 F.

16. In the treatment of petroleum oils, the process which comprises continuously distilllng ofi' vapors from a boiling body of hot high boiling oil containing aluminum chlorid, cooling said vapors to a tempera- 'to a temperture not substantially above 350 F and returning the condensate from such cooled vapors to the body for further treatment and removing the cooled vapors.

18. In the treatment of petroleum oils,

the process which comprises maintaining a body of high boiling oil containing aluminum chlorid at a :boiling temperature around 500? F., removing vapors therefrom and cooling said vapors to about'350 F. and returning matters condensed in said cooling to said body. 19. The process of converting higher boil- 1ng petroleum oils into lower boiling oil which comprises heating a mixture of such a higher boiling oil and aluminum chlorid to distillation temperature, allowing the vapor products of the reaction to pass to a condenser, maintaining the condenser at a temperature not substantially above 300 F., and passing vapors not condensed at this temperature from said condenser to a final condenser for condensation.

20. In the conversion of oils, the process which comprises heating to ebullition a body of high boiling oil with aluminum chlorid to a temperature below 600 F., the vapors of catalytically produced lower boiling bodies being removed substantially as fast as such bodies are formed while continuously returning condensed vapors of higher boiling bodies and of aluminum chlorid.

21. In the \conversion of oils, the process which comprises heating a body of high boiling oil with aluminum chloride to a temperature of. about 500 .F., to produce ebullition, the vapors of catalytlcally produced lower boiling bodies being removed substantially as fast as such bodies are formed while continuously returning condensed vapors of higher boiling bodies and of aluminum chlorid.

22. The process of converting higher boiling patroleum oils into lower boiling oil which comprises'heating a mixture of such a higher boiling oil and aluminum chlorid to a temperature not substantially above 600 F., while removing and condensing vapors of lower boiling oil formed thereby.

23. The process of converting higher boiling petroleum oils into lower boiling oil which comprises heating a mixture of such a higher boiling'oil and aluminum chlorid to temperatures not substantially above 600 F. anddurin such heating condensing and separately co lecting the lower boiling oils produced thereby.

24:. The process of converting gas oil or fuel oil into lower boiling oil which comprises heating the gas oil or fuel oil together with aluminum chlorid to temperatures around 500550 F., while removing and -condensing vapors of lower boiling oil formed thereby.

25. The process of converting gas oil or fuel oil into lower boiling oil which comprises heating the gas oil or fuel oil together with aluminum chlorid to temperatures .around 500550 F. and during such heating separately condensing and collecting the lower boiling oil produced thereby.

28. The process of producing kerosene and gasoline from petroleum oils having boiling points higher than either which comprises heating such a higher boiling point oil in the presence of aluminum chlorid to distillation temperature, and during such heating condensing the vapors of kerosene and gasoline produced thereby.

27. The process of producing kerosene and gasoline from petroleum oils having boiling points higher than either which comprises heating such a higher boiling point oil in the presence of aluminum chlorid to distillation temperature, and during such heating together condensing the vapors of kerosene and gasoline produced thereby, and then separating the gasoline and kerosene.

'28. In the distillation of petroleum oils with aluminum chlorid, the process which comprises establishing and maint'alnin a body of such oil and of aluminum chlori at distilling temperature and supplying hot.

oil to such body.

29. In the treatment f p roleum oils, the distillation temperature, separating vaporsmagma process which comprises continuously distilling ofl' 'low boiling vapors from a boiling body of high boilingoil containing aluminum chlorid and continuously supplychlorid in said body, the volume of said oils produced by the catalytic action of said body being kept substantially constant during said heating operation by additions of high boiling oil in amounts corresponding to the amounts of low boiling products re moved. v

31. The process of converting hi h boiling petroleum oils into lower 'boi ing oil which comprises heating such a higher boiling oil together with aluminum chlorid to distillation temperature, separating vapors of lower boiling oil formed from higher boiling oil, condensing the lower boiling oil and adding oil 'and aluminum chlorid to the body undergoing. distillation.

32. In the continuous conversion of higher boiling petroleum oils into lower boiling oils, the process which comprises establishing and maintaining a boiling body of such higher boiling oil in the presence ofaluminum chlorid while constantly removing vapors of lower boiling oils produced by the action of such aluminum chlorid, the volume of said body being maintained substantially constant by additions of higher boiling oil during the operation and exhausted aluminum chlorid being removed from such oil from time to time and replaced by additions of active aluminum chlorid.

33. The process of converting higher boiling petroleum oils into lower boiling oils' which comprises heating such a higher boiling oil together with aluminum chloridto distillation temperature, separating vapors of lower boiling oil formed from higher boiling oil, condensing the lower boiling oil and adding high boiling oil and aluminum chlorid admixed therewith-to thebody of oil undergoing distillation.

34. The process of converting higher boil in petroleum oils into lower boiling 'oils w ich comprises heating such a higher boil- I which comprises heating such a higher boiling oil together with aluminum chlorid to of lower boiling oil formed higher boiling oil, condensing the lower boiling oil and adding hot oil and aluminum chlorid adchlorid passes into a coky matter, said coky matter being removed from the oil when its activity lessens and replaced with active aluminum chlorid. I I v 37. The process of converting higher boiling petroleum oils into lower boiling 011s whic distillation temperature, separating vapors of lower boiling oil 'formed from higher boiling oil, condensing the lower boiling oil and adding vapors of aluminum chlorid to the body undergoing distillation.

38. The process of convertin higher boil ing petroleum oils into lower boiling oils which comprises distilling such a higher boiling oil in admixture with aluminum chlorid, condensing the lower boiling. oil produced and during distillation withdrawing residual aluminum chlorid from the body of higher 'boiling'oil. v

39. The process of converting higher boiling etroleum oils into lower boiling oils whic comprises admixing such a higher boilin oil with partially spent aluminum chlori which has been used in previous treatment of oils, heating to a distillation temperature, and condensing the lower boiling oil reduced. a 1

40. T e process of converting higher boiling petroleum oils into lower boiling oils which comprises distilling such a higher boilin oil in the presence of aluminum chlori during the distillation, collecting and condensing vapors of lower boiling oil produced, and then gradually raisin the temperature of the .higher boiling oi and the aluminum chlorid undergoing distillation as the lower boiling oil is condensed.

41. In the conversion of high boiling oils, the process which comprises heating a charge'of aluminum chlorid in contact with a constant volume of oil for a period of not less than 48 hours, the low boiling productsproduced in such heating being removed substantially as fast as formed and the constant volume of oil being preserved by ad ditions of new oil.

42. The process of converting higher boiling petroleum oils into lower boiling oils which comprises heating such a higher boiling oil together with aluminum chlorid to distillation temperature, separating vapors of lower boiling oil formed from higher boiling oil, condensing vapors of lower boil-- comprises heating such a higher heiling oil together with aluminum chlorid to whic ing oil formed,.and a itating the mixture of higher boiling oil an aluminum chlorid undergoing distillation; I

43. In the conversion of oils, the process which comprises boiling a body of oil in the presence of aluminum chlorid undercontinuous agitation, the volume of such oil being kept replenished by additions of high boliling oil to compensate for volatilized 01 s.

44. In the conversion of oils, the process which comprises heating a constantly replenished boiling body of such oil with a charge of aluminum chlorid with constant agitation until the aluminum chlorid loses its high activity and tends to settle out as a coky mass.

45. The process of converting higher boiling petroleumoils into lower boiling oils which comprises heating such a higher boiling oil together with from 1 to 5 per cent of aluminum chlorid to distillation temperature, separating vapors of lower boiling oil formed from higher boiling oil, condensing vapors of lower boiling oil formed, and agitating the mixture of higher boiling oil and aluminum chlorid undergoing distillation.

46. The process of converting higher boiling petroleum oils into lower boiling oils which comprises heating such a higher boiling oil together with about 5 per cent of aluminum chlorid to distillation temperature, separating vapors of lower boiling oil formed from higher boiling oil, condensing vapors of lower boiling oil formed, and agitating'the mixture of higher boiling oil and aluminum chlorid undergoing distillation.

47. The process of converting higher boil- 7 49. The process of converting higher boil- A120 ing petroleum oils of the nature of fuel oil or gas oil into lower boiling oils which comprises heating such fuel oil or gas oil to distillation temperature with aluminum chlorid and as distillation proceeds condensing the lower boiling oil produced by such heating.

50.. The process of producing gasoline from higher boiling petroleum oils which comprises distilling such a higher boiling oil in the presence of aluminum chlorid and,

during the distillation condensing the gasoline vapors produced thcreb 51. The process of converting higher boiling petroleum oils into lower boiling oils which comprises heating such a higher boiling oil in admixture with aluminum chlorid to distillation temperature, condensing the lower boiling oil produced, removing the aluminum chlorid from the said mixture, and treating additional higher boiling petroleum oil with said removed aluminum chlorid at a distillation temperature.

52. The process of converting higher boiling petroleum oils contaiiaing sulfur into lower boiling oils which comprises distilling such a higher boiling oil in the presence of aluminium chlorid and during the distillation condensing the lower boiling oil formed thereby.

53. The process of converting higher boiling petroleum oils containing sulfur into lower boiling oils which comprises treating such a higher boiling oil with sulfuric acid to remove the sulfur and to dry it, heating the sulfur-free and dry products of such treatment with aluminum chlorid to distilwhich comprises distilling such a higher boiling oil in the presence of aluminumchlorid in a still, collecting the vapors of lower boiling oils produced, passing the higher boiling oils to a second still, distilling such higher boiling oils therein with aluminum chlorid and collecting from said second still the lower boiling oil produced.

56. The process of converting higher boiling'petroleum oils into lower boiling oils which comprises distilling the same in the presence Offllllllllllum chlorid in a still, condensing the vapors of lower boiling oils produced, passing the higher boiling oils to another still and distilling the same therein with a larger percentage of aluminum chlorid than was used in the first distillation, and collecting the vapors of lower boiling oils produced in the second distillation.

57. The process of converting higher boiling petroleum oils into lower boiling oils which comprises passing such a higher boiling oil in admixture with aluminum chlorid through a plurality of stills distilling the mixture in each such still, an collecting the lower boiling oil produced in each such still.

58. The process of converting higher boiling petroleum oils into lower boiling oils in a plurality of stages, which comprises heatin such oils in the presence ofalumi'num ch orid in each-such stage to distillation temperature, collecting the vapors of lower boiling oils produced from each such stage and.

ing such a higher boiling oil in the presence of aluminum chlorid in each such stage to,

distillation temperature, collecting the va pors of lower boiling oil produced from each such stage and passing h'igher boiling oils together with some a uminum chlorid admixed with the oil to a succeeding stage, but leavin settled aluminumchlorid in admixture with the oil in -the preceding stage.

60. The process of converting petroleum hydrocarbons having higher-boiling points into naphtha, which consists in heating a mixture of said hydrocarbons and anhydrous aluminum chlorid to a temperature producing vapor of a lower boiling oil having an end-boilin point not substantially above the end-bolling point of naphtha and maintainin the mixture atsuch temperature.

61. he process of converting petroleum hydrocarbons having higher-boiling points into oils having lower-boiling points, which consists in heating a mixture of said hydrocarbons and anhydrous aluminumchlorid to a temperature producing vapor of a lower boiling oil having an end-boiling point not substantially above the end-boiling point of illuminating oil and maintaining the mixture at such temperature.

62. The process of converting petroleum hydrocarbons having higher-boiling points into naphtha, which consists in heating a mixture of said hydrocarbons and anhydrous aluminum chlorid to a temeprature producing vapor of a lower boiling oil having an end-boiling point not substantially above the end-boiling point of naphtha and maintain-- ing the mlxture at such temperature until the greater part of the oil has been converted into naphtha.

' 63. The process of converting petroleum hydrocarbons having higher-boiling points into oils having lower-boiling points, which consists in heating a mixture of said hydrocarbons and anhydrous aluminum chlorid to a temperature producing vapor of lower boiling oil having an end-boilingpoint not substantially above the end-boiling point of illuminating oil and maintaining the mixture at such temperature until the greater part. of the oil has been converted into.

naphtha and illuminating oil.

64. The process of converting petroleum I hydrocarbons having higher-boiling points iao 30 into oils having lower-boiling consists in heating a mixture such hydra cc nating oil, condensing carbons and anhydrous aluminum chlorid to.

a temperature producing vapor of lowerboiling oil having an end-boiling point above the end-boiling point of naphtha, but below' the end boilingpoint of illuminating oil,

maintaining the mixture .at-such temperature, condensing oils of the character of illuminating oil driven off in a preliminary cooling chamber, and conducting the naphtha driven off to a condenser.

65. The process of converting petroleum hydrocarbons having higher-boiling points into naphtha, which consists in heating a mixture of said hydrocarbons and anhydrous aluminum chlorid to a temperature producing vapor of lower boiling oil having an end-boiling point above the end-boiling point of naphtha, but below the end-boiling pointof illuminatin oil, condensing oil of the character of i uminating oil driven oii in a preliminary cooling chamber, returning said oil to the still to be further acted on whereby higher-boiling oil is converted into naphtha and conducting the naphtha driven off to a condenser. D 66. The process of converting petroleum hydrocarbons having higher-boiling points ints, which carbons and anhydrous aluminum chlorid to a temperature producing vapor of lower boiling oil having an end-boiling point 85 above the end-boiling point of naphtha, but

below the end-boiling point of illuminating oil, maintaining the mixture at such temperature until the greater part of the oil has been converted into naphtha and illumioil of the character oil driven oii in a prelimiof illuminatin amber, and conducting the nary cooling naphtha driven 0E to a condenser.

petroleum 4 hydrocarbons having higher-boiling points 67. The proces of convertin into naphtha, which consists in heatin a mixture of said hydrocarbons and an ydrous aluminum chlorid to a temperature producing vapor of lower boiling oil having an end-boiling point above the end-boiling point of naphtha but below the end-boiling point of illuminating oil, condensing oils of the character of illuminating oil driven ofi in a preliminary coo-ling chamber, returncfiing said oils to the still to be further acted on, whereby the greater portion of the higher-boiling oil is converted into na htha, and conducting the naphtha driven o to a condenser.

68. The p of converting higher boilwith the aid of aluminum chlorid which comprises heating such a higher boiling oil in the presence of aluminum chlorid to a temperature higher than the end boiling point of the lower boilin oil desired, but not substantially hi her an the end boiling point of the hig ier boiling oil operated upon, and removing and condensing vapors of the lower boiling oil produced.

70. The process of converting hi her boiling petroleum oil into asoline wit the aid of aluminum chlorid wiich comprises heating a mixture of such a higher boiling oil and aluminum chlorid to a temperature above the end-boiling point of gasoline, and while heating collectlntg and condensing the vapors of gasoline pro uced thereby.

71. process of converting petroleum oils of relatively high boiling points into products of lower bolling ints which comprises treating said oils with ing the hydrocarbon addition products of a halogen aluminum compound.

72. A process which comprises heatin petroleum hydrocarbon materials ofrelatively high boiling points with a'hydrocarbon derivative of an aluminum halid com und, and distilling ofi' products of lower iling point than the starting material.

73. In the process of treating petroleum hydrocarbon oil with a catalyzer com rising a halogen aluminum h drocarbon a dition plroduct the step of owing an inflow of esh material in order to make the process continuous.

74:. In the treating of mineral oils or their distillates with a catalyzer the step of in-.

ALMER M. MQAFEE.

Witnesses K. P. MoEilRoY, Gnome MODANIEL.

a catalyzer compris- 

